Reduction of a Redox-Active Ligand Drives Switching in a Cu(I) Pseudorotaxane by a Bimolecular Mechanism
The reduction of a redox-active ligand is shown to drive reversible switching of a Cu(I) [2]pseudorotaxane ([2]PR{sup 2+}) into the reduced [3]pseudorotaxane ([3]PR{sup 2+}) by a bimolecular mechanism. The unreduced pseudorotaxanes [2]PR{sup 2+} and [3]PR{sup 2+} are initially self-assembled from the binucleating ligand, 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine (Me2BPTZ), and a preformed copper-macrocycle moiety (Cu-M{sup 2+}) based on 1,10-phenanthroline. X-ray crystallography revealed a syn geometry of the [3]PR{sup 2+}. The UV-vis-NIR spectra show low-energy metal-to-ligand charge-transfer transitions that red shift from 808 nm for [2]PR{sup 2+} to 1088 nm for [3]PR{sup 2+}. Quantitative analysis of the UV-vis-NIR titration shows the stepwise formation constants to be K{sub 1} = 8.9 x 10{sup 8} M{sup -1} and K{sub 2} = 3.1 x 10{sup 6} M{sup -1}, indicative of negative cooperativity. The cyclic voltammetry (CV) and coulometry of Me{sub 2}BPTZ, [2]PR{sup 2+}, and [3]PR{sup 2+} shows the one-electron reductions at E{sub 1/2} = -0.96, -0.65, and -0.285 V, respectively, to be stabilized in a stepwise manner by each Cu{sup 2+} ion. CVs of [2]PR{sup 2+} show changes with scan rate consistent with an EC mechanism of supramolecular disproportionation after reduction: [2]PR{sup 0} + [2]PR{sup 2+} = [3]PR{sup 2+} + Me{sub 2}BPTZ{sup 0} (K*{sub D}, k{sub d}). UV-vis-NIR spectroelectrochemistry was used to confirm the 1:1 product stoichiometry for [3]PR{sup 2+}:Me{sub 2}BPTZ. The driving force ({Delta}G*{sub D} = -5.1 kcal mol{sup -1}) for the reaction is based on the enhanced stability of the reduced [3]PR{sup 2+} over reduced [2]PR{sup 0} by 365 mV (8.4 kcal mol{sup -1}). Digital simulations of the CVs are consistent with a bimolecular pathway (k{sub d} = 12,000 s{sup -1} M{sup -1}). Confirmation of the mechanism provides a basis to extend this new switching modality to molecular machines.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1005517
- Journal Information:
- J. Am. Chem. Soc., Vol. 131, Issue (3) ; 01, 2009; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- ENGLISH
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